EP3827966A1 - Produits formés par fabrication de formes libres solides et procédé de fabrication - Google Patents

Produits formés par fabrication de formes libres solides et procédé de fabrication Download PDF

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Publication number
EP3827966A1
EP3827966A1 EP20210365.1A EP20210365A EP3827966A1 EP 3827966 A1 EP3827966 A1 EP 3827966A1 EP 20210365 A EP20210365 A EP 20210365A EP 3827966 A1 EP3827966 A1 EP 3827966A1
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EP
European Patent Office
Prior art keywords
hydrogel
solid freeform
freeform fabrication
fabrication product
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20210365.1A
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German (de)
English (en)
Inventor
Takuya Saito
Takashi Matsumura
Tatsuya Niimi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
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Ricoh Co Ltd
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Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Publication of EP3827966A1 publication Critical patent/EP3827966A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0009—Making of catheters or other medical or surgical tubes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/145—Hydrogels or hydrocolloids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09B—EDUCATIONAL OR DEMONSTRATION APPLIANCES; APPLIANCES FOR TEACHING, OR COMMUNICATING WITH, THE BLIND, DEAF OR MUTE; MODELS; PLANETARIA; GLOBES; MAPS; DIAGRAMS
    • G09B23/00—Models for scientific, medical, or mathematical purposes, e.g. full-sized devices for demonstration purposes
    • G09B23/28—Models for scientific, medical, or mathematical purposes, e.g. full-sized devices for demonstration purposes for medicine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing

Definitions

  • the present invention relates to a solid freeform fabrication product and a method of manufacturing a solid freeform fabrication product.
  • Vascular surgery includes treatment of swollen parts (aneurysm) and shunt, cutoff, and anastomosis of blood vessels.
  • Catheter serving as an instrument having a wire-like form is intubated into a blood vessel in many cases of vascular surgery. Such insertion of catheter requires training for medical procedures (surgical technique). Animals or blood vessel models are used in the training if a human body is not used.
  • a vessel model has been proposed in JP-5140857-B1 ( JP-2009-273508-A1 ) in which blood vessel film added by data processing is fabricated on the surface of the form data of three-dimensional blood flow by additive manufacturing or a catheter operation simulator has been proposed in JP-6385664-B1 ( JP-2015-69054-A1 ) which is formed from transparent materials.
  • a hydrogel structure has been proposed in JP-2018-178069-A1 which has a hollow tubular structure made from materials having a high transmission.
  • JP-5140857-B1 JP-2009-273508-A1
  • JP-2009-273508-A1 The structure of JP-5140857-B1 ( JP-2009-273508-A1 ) mentioned above has a structure A in the present disclosure so that a model having a massive dead weight cannot hold itself. As a result, it is not possible to achieve the original objective for training procedures because the model deviates from desired three-dimensional data.
  • JP-6385664-B 1 JP-2015-69054-A1
  • JP-6385664-B 1 JP-2015-69054-A1
  • the structure of JP-6385664-B 1 is formed of a laminate of plate-like imitated vessel flow path layers so that as the number of plates to be stacked increases if the plate-like imitated vessel flow path is a solid form, the thickness of the solid form increases. This increase in the thickness does not affect the visibility of the solid form when viewed from top. However, it significantly degrades visibility when viewed obliquely because the distance to the vessel flow path increases or the side of a plate overlaps the vessel flow path.
  • JP-2018-178069-A1 incurs deformation by dead weight in the case of the structure A alone.
  • the structure has a block having a hollow tubular structure, the thickness between the top portion and the hollow portion is not uniform so that the model has a portion with poor visibility.
  • an improved solid freeform fabrication product which deforms on stress and provides good visibility to the hollow parts inside the solid freeform fabrication product when viewed from top or in an oblique direction, and is suitable as a model such as a vessel model for practicing procedures for surgical operation with a jig with which a hollow structure is pierced.
  • a solid freeform fabrication product (100) which includes a structure A (26) containing a soft material and having a hollow portion H (21;24) inside and a structure B (27) holding the structure A (26), wherein the layer between the structure A (26) and the hollow portion H (21;24) has a uniform thickness when the solid freeform fabrication product (100) is viewed from top.
  • image forming, recording, printing, modeling, etc. in the present disclosure represent the same meaning, unless otherwise specified.
  • the solid freeform fabrication of the present disclosure has a structure A containing a soft material and having a hollow portion H inside and a structure B holding the structure A, wherein the ring structure formed between the structure A and the hollow portion H viewed from top has a uniform thickness.
  • the structure A and the structure B may be integrated or separable.
  • the structure A and the structure B may be formed as an integrally molded unit.
  • the structure A and the structure B can be fabricated separately and combined to obtain the solid freeform fabrication product of the present disclosure.
  • the solid freeform fabrication product of the present disclosure is formed of a combination unit of the structure A and the structure B.
  • the structure A includes blood vessels and lymph channels or a part of an organ connected to them and the structure B supports the structure A as a pedestal.
  • the structure A and the hollow portion H forms a film having a uniform thickness when viewed from the opposite side of the structure B, that is, the side on which the structure is exposed to the outside.
  • the structure A includes a model having a part a uniform thickness added around the hollow portion H. Such a model has a uniform thickness.
  • the solid freeform fabrication product of the present disclosure has three features.
  • the first feature is that the structure A deforms in response to an external force like a real organ and demonstrates flexibility owing to the soft material contained in the structure A.
  • the second feature is that the structure A can hold the original shape regardless of dead weight because the structure B supports the structure A. If the structure A is displaced by an external force, the structure A readily returns to the original position when the external force is released.
  • the third feature is that the visibility of the hollow portion H is the same even if the angle of view (projection angle of the focused surface from perspective) increases because the thickness of the film present between the structure A and the hollow portion H on the top part is uniform when a plane T in contact with the structure B is defined as the bottom surface.
  • the soft material contained in the structure A is not particularly limited as long as it has a shore A hardness of 35 or less.
  • hydrogels include, but are not limited to, soft resins such as polyurethane, acrylic rubber, silicone rubber and hydrogels such as polyvinyl alcohol, polyacrylamide, and polyacrylic acid. Hydrogels are preferable because its texture is similar to that of a live body.
  • the hydrogel represents a gel including water as the main component.
  • the hollow portion H is not particularly limited and is preferably an inner cavity formed in a live body.
  • the hydrogel preferably contains one of artery, vena, and lymph channel in particular to insert medical equipment in a tube. The most preferable is an artery usable for training for procedures with a catheter.
  • Such an artery preferably has a hollow portion having a diameter of from 2.0 to 0.5 mm to practice procedures for surgical training with a catheter.
  • the hollow portion H can be used to confirm whether a catheter having a diameter in the range mentioned above can be inserted into a tube because the hollow portion of a live body is not truly cylindrical.
  • the hollow portion can be mechanically measured by an instrument such as caliper. Also, it can be measured utilizing a microscope or a one-shot 3D form measuring device (for example, device available from KEYENCE CORPORATION).
  • From top means the direction along which the model is viewed most frequently during the procedures for surgical training. In a real operation, the field of a doctor is limited in a particular direction in most cases.
  • doctors can obtain only a perspective obtained by the incision.
  • the perspective of doctors is limited to the vision of a camera in the case of laparoscopy or endoscope.
  • Observation by X radiation is limited to the incidence angle of the X radiation or the detection direction.
  • the training effect is boosted by the training for procedures because the direction obtained in a real operation can be obtained.
  • the catheter When a catheter is inserted into coronary artery, the catheter is located based on signals obtained as a result of irradiation of X radiation in a real operation.
  • the position of a catheter can be visibly confirmed by a training model without using X radiation, it is preferable that the catheter be located from any direction.
  • the irradiation angle of X radiation can be changed by scanning.
  • the position of the catheter is visible from directions in a range of from approximately +60 degrees to approximately -60 degrees (22 illustrated in FIG. 1 ) by swinging instead of a single direction (23 in FIG. 1 ) alone.
  • the obtained information is close to that in a real operation.
  • the hollow portion can be recognized in a range of from +60 degrees to -60 degrees instead of a single direction alone in the case of laparotomy and laparoscopy by swinging the view or a camera in a similar manner, the training becomes similar to a real operation.
  • the uniform thickness in the present disclosure means that the value of the film thickness is within 25 to 400 percent of the average of the film thickness when the film thickness represents the thickness of the tubular structure formed by the structure A and the hollow portion H when viewed from top. This is because the film thickness changes over time in the range mentioned above owing to swelling or drying even if the film is evenly formed on the basis of the original fabrication data.
  • the thickness of the cross sections at t1, t2, t3, t4, and t5 perpendicular to a hollow portion 24 of a structure is measured as the film thickness as illustrated in FIG. 2 .
  • the film thickness of the cross section crossing the structure at an angle of 60 degrees (t1n, t3n, where n represents an integer, specifically t11, t12, t13, t14, and t15, and t31, t32, t33, t34, and t35) to the perpendicular direction is also measured in addition to the perpendicular direction (t2n, where n represent an integer, specifically t21, t22, t23, t24, and t25).
  • the structure is cut to measure the film thickness thereof with caliper, micrometer, or microscope, with a one shot 3D form measuring device.
  • the solid freeform fabrication product furthermore include a portion of the soft material mentioned above having a moisture content of 50 percent or more, the soft material contain a mineral and a polymer, and the solid freeform fabrication product be formed of a hydrogel enclosing water in a three-dimensional network structure formed of a complex of the mineral and the polymer.
  • the hydrogel represents a gel including water as the main component.
  • the structure A and the structure B holding the structure A may be separable or inseparable.
  • both structures can be separated from each other, the hollow portion H can be observed in all directions and the structure A can be held free of deformation when combined with the structure B.
  • the unit can be an inseparable set.
  • the structure A is held by the structure B accordingly and free of deformation owing to its dead weight.
  • both structures can be formed inseparably integrated. If the border between the structure A and the structure B is not visible, visibility of the structures from oblique angles is enhanced.
  • the structure A and the structure B be integrally molded. If a complicated structure A and a structure B that can readily hold the structure A are separately molded to manufacture a solid freeform fabrication product, it is highly likely that either or both of the structure A and the structure B is broken when the structure A and the structure B are combined. Once combined, it is difficult to separate from each other. If the structure A and the structure B are integrated at the time when the data as the base of the form (also referred as "original fabrication data") of a fabrication product is created, the border surface is invisible in the solid freeform fabrication product of the present disclosure so that the visibility of the product tends to be good. During fabrication by a 3D printer, the original fabrication data is referred so that multiple structures combined in a complicated manner can be integrally fabricated.
  • the structure B is preferably free of eaves structures.
  • Eaves structures may have an adverse impact on the fabrication product. In the cast molding, such an eaves structure caught when removed, which may damage the product.
  • the eaves structure requires a support. When the support is removed, it raises a concern about increasing the roughness of the surface of the product.
  • Free of eaves means that, as illustrated in FIG. 3 , when a structure A 26 is orthogonally projected onto a plane T in contact with a structure B 27, the figure formed on the plane T is defined as a figure S and when a figure created by intersections of perpendiculars from the plane T onto the structure A 26 is defined as a figure S', the solid enclosed by the figure S and the figure S' is free of voids.
  • the training for surgical procedures using the solid freeform fabrication product of the present disclosure uses either or both of catheter and endoscope.
  • the catheter has no particular limit and can be suitably selected to suit to a particular application.
  • catheter for angiography balloon catheter, cerebral blood vessel catheter, cancer catheter curing, indwelling vascular catheter, indwelling suction catheter, and urethral indwelling catheter are suitable.
  • the endoscope has no specific limit and can be suitably selected to suit to a particular application.
  • throat cavity endoscope, bronchoscope, upper gastrointestinal endoscope, duodenoscope, enteroscope, large intestine endoscope, thoracoscope, cystoscope, cholangioscope, and angioscope are usable.
  • the solid freeform fabrication product of the present disclosure can be suitably applied to training for surgical procedures of catheter intubation or a simulation before surgery.
  • the training for surgical procedures of catheter intubation means a practice to insert a catheter into a blood vessel model and cause it to reach a target location.
  • This training includes changing the thickness of a catheter to suit to a particular application and providing a stent, wire, and a balloon at a distal end to use it for treatment at an assumed affected part.
  • Selecting the optimal catheter to suit to the shape of blood vessel is a part of the training.
  • a combinational use of the solid freeform fabrication product of the present disclosure with one or more catheters is beneficial.
  • Such a training provide a texture similar to that of the inside of a real blood vessel.
  • the solid freeform fabrication product of the present disclosure suitably deforms upon an application of an external force and returns to the original state when the external force is released.
  • the product is expected to be highly effective because the product can show the complicated hollow portion with good visibility from different angles.
  • it is also suitable to provide a mechanism that lets liquid flow in the hollow portion to offer a training situation in which blood is flowing.
  • Lubricants can be optionally used to make the texture of the insertion of a catheter or endoscope into a hollow portion real as if a live body is used. It is possible to adjust the texture achieved when a catheter or endoscope is inserted into a hollow portion by applying a surfactant that can be used in a solvent, oil, and a lubricant for wet type wire drawing. These additives can be applied to the inner wall of a structure in contact with the hollow portion or let flow in a tube in a liquid form.
  • the solvent has no particular limit and can be suitably selected to suit to a particular application.
  • water and an organic solvent are usable. These can be used alone or in combination. Of these, organic solvents are preferable to prevent them from being absorbed in the solid freeform fabrication product of the present disclosure. Solvents having high boiling points are preferable to prevent drying when the soft material contains water.
  • the oil mentioned above has no specific limit and can be suitably selected to suit to a particular application.
  • synthetic oil such as mineral oil and silicone, vegetable oil, wax, and animal oil are usable.
  • the surfactant mentioned above has no particular limit and can be suitably selected to suit to a particular application.
  • anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants are usable. These can be used alone or in combination.
  • the nonionic surfactant has no particular limit and can be suitably selected to suit to a particular application.
  • polyoxyethylene alkyl ether polyoxyethylene alkyl phenylether, polyoxyethylene alkyl phosphoric acid ester, polyoxyethylene aliphatic acid ester, sorbitan aliphatic acid ester, polyoxyethylene sorbitan aliphatic acid ester, aliphatic acid monoglyceride, sucrose aliphatic acid esters, and higher aliphatic acid alkanol amide.
  • the anionic surfactant has no particular limit and can be suitably selected to suit to a particular application.
  • alkyl sulfate alkyl sulfate ether, alkyl sulfate amide ether, alkyl sulfate aryl polyether, sulfuric acid monoglyceride, alkyl sulfonate, alkylamide sulfonate, alkylaryl sulfonate, olefin sulfonate, paraffin sulfonate, alkyl sulfo succinate, alkylether sulfo succinate, alkylamide sulfo succinate, alkyl succine amide acid, alkyl sulfo acetate, alkyl phosphate, alkyl phosphate ether, acyl sarcosine, acyl isethionate, and acyl-N-acyl taurine.
  • the cationic surfactant has no particular limit and can be suitably selected to suit to a particular application.
  • Specific examples include, but are not limited to, distearyl dimethylammonium chloride, stearyldimethyl benzylammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, myristyldimethyl benzyl ammonium chloride, ethyl acetate lanoline aliphatic acid amino propylethyl dimethylammonium, dicocoyl dimethylammonium chloride, lauryl trimethylammonium chloride, and ethyl sulfate branched aliphatic acid aminopropyl ethyldimethyl ammonium.
  • amphoteric surfactant has no particular limit and can be suitably selected to suit to a particular application.
  • Examples are amide amino acid type amphoteric surfactants having an alkyl group, alkenyl group, or acyl group having 8 to 24 carbon atoms, imidazoline type amphoteric surfactant of secondary or tertiary amides, carbobetaine-based, amide betaine-based, sulfobetaine-based, hydroxy sulfobetaine-based, or amidesulfo betaine-based amphoteric surfactants having an alkyl group, alkenyl group, or acyl group having 8 to 24 carbon atoms.
  • Specific examples include, but are not limited to, 2-alkyl-N-carboxydimethyl-N-hydroxyethylimidazolinium betaine, staryldihydroxyethylbetaine, laurylhydroxysulfobetaine, bis(stearyl-N-hydroxyethyl imidazokine)chloroacetate complex, lauryldimethylamino betaine acetate, cocoylamide propyl betaine, and cocoyl alkylbetaine.
  • the structure B is manufactured to hold the structure A as a live body model.
  • One way of manufacturing the form of the structure B is as follows. 3D data editing software such as MAGICS (created by Materialise NV) is used to edit data.
  • the 3D data about the structure A is obtained.
  • the 3D data of the structure A having the hollow portion H is suitable.
  • the data of the hollow portion H is obtained to add a uniform thickness by data editing.
  • the direction of the structure A is determined.
  • “from top (top view)” is determined as the direction in which the model is viewed most frequently during training for surgical procedures.
  • FIGS. 4A and 4B are diagrams illustrating the structure A 31 as a live body model including aortic valve and coronary artery of a heart and RCC represents right semilunar cusp of aortic valve, NCC represents non-coronary cusp of the aortic valve, and LCC represents a left semilunar cusp of aortic valve.
  • FIG. 4A is a diagram illustrating a side view of the structure A 31 and FIG. 4B is a diagram thereof from top.
  • the direction indicated by an arrow 32 is the most frequently viewed direction during the training for surgical procedures.
  • FIG. 5A is a diagram illustrating the structure A 31 and the cuboid R1 33 viewed from top
  • FIG. 5B is a diagram illustrating the structure A 31 and the cuboid R1 33 viewed from side.
  • One of the surfaces of the cuboid R1 33 is necessary to be perpendicular to the top of the structure A 31.
  • the structure A 31 is overlapped on the cuboid R1 33 and the portion having neither the structure A 31 and the cuboid R1 33 from top is deleted (booleaned). This deletion is to reduce the extra fabrication portions that prevent visions to enhance visibility of the inside.
  • the structure A 31 is overlapped on the cuboid R1 33 as illustrated in FIGS. 6A and 6B .
  • the cuboid R1 33 is divided along the line passing through the structure A 31 viewed from the surface (side of the cuboid R1) parallel to the top among the surfaces of the cuboid R1 33 and the top half of the divided cuboid R1 33 is deleted to obtain a pedestal P1 34.
  • FIG. 6A is a diagram illustrating a perspective view of a set of the structure A 31 and the pedestal P1 34 and FIG. 6B is a diagram illustrating the set viewed from side.
  • FIG. 7A is a diagram illustrating a perspective view of a set (solid freeform fabrication product) 100 of the structure A 31 and the pedestal P1 34 and
  • FIG. 7B is a diagram illustrating the set 100 viewed from side.
  • the form of the structure B is obtained by merging the pedestal P1 34 and the cuboid R2 35 followed by boolean of the structure A 31 and the hollow portion H.
  • the structure A 31 and the structure B are merged, the structure A 31, the pedestal P1 34, and the cuboid R2 35 are merged followed by boolean of the hollow portion H.
  • the object that forms the pedestal is a cuboid but is not particularly limited as long as the surface on the top side and the surface opposite thereto are parallel to each other.
  • Objects having a cylindrical form, truncated cone, insert form, and n polygonal column can be used. It is preferable that the surface on the top side from top does not protrude from the side opposite thereto when a truncated cone or insert form is used.
  • Data required for training for surgical procedures may be optionally edited.
  • This data editing includes a hole connecting with the hollow portion H and forms and film thickness to adjust difficulty.
  • the optimal material most suitable as the soft material is hydrogel.
  • Hydrogels are hydrophilic like live bodies and may have a moisture content of as high as from 80 to 90 percent, which is a moisture content of live bodies so that the textures, inside structure, and feeling of use can be made similar to those of organs of human bodies. Hydrogels are classified into gels derived from natural products such as gelatin, agar, and carrageen moss and synthetic gels such as polyvinyl alcohols, polyacrylicamides, and polyacrylic acids. The moisture content of the hydrogel is preferably from 50 to 98 percent by mass and more preferably from 60 to 97 percent by mass. A moisture content less than 50 percent by mass provides texture like that of a resin. In contrast, products having a moisture content greater than 98 percent by mass are too soft to hold the form on its own. Both are away from a real organ.
  • a moisture content of from 60 to 97 percent by mass provides a texture like that of a real organ.
  • the moisture content can be measured using, for example, a (heating and drying) moisture analyzer (MS-70, manufactured by A&D Company, Limited).
  • MS-70 heating and drying moisture analyzer
  • the hydrogel furthermore include a mineral and a polymer and be formed of a hydrogel enclosing water in a three-dimensional network structure formed of a complex of the mineral and the polymer.
  • a hydrogel has a high degree of clearness and flexibility.
  • water, polymers, mineral, organic solvents, and other components are mixed by a suitable method to produce ink as hydrogel precursor. Thereafter, this ink is cured by a suitable method to prepare a hydrogel.
  • the polymer there is no specific limit to the polymer and a suitable polymer is selected to suit to a particular application.
  • a suitable polymer is selected to suit to a particular application.
  • water-soluble polymers are preferable because the hydrogel includes water as the main component. Since the water-soluble polymer is contained, it is possible to maintain the strength of a hydrogel containing water as the main component.
  • Water-solubility of the water-soluble polymer means that, for example, when 1 g of the water-soluble polymer is mixed with 100 g of water and stirred at 30 degrees C, 90 percent by mass or more of the polymer is dissolved in water.
  • polymers having, for example, an amide group, an amino group, a hydroxyl group, a tetramethyl ammonium group, a silanol group, an epoxy group, etc. are suitable.
  • Homopolymers monopolymer
  • heteropolymers copolymers
  • monopolymer monopolymer
  • known functional groups can be introduced into these.
  • the polymer may take a salt form. Of these, homo polymers are preferable.
  • the polymer can be obtained by polymerizing a polymerizable monomer.
  • the polymerizable monomer is described in the method of manufacturing a hydrogel structure, which is described later.
  • the water-soluble polymer is prepared by polymerization of a polymerizable monomer.
  • a polymerizable monomer include, but are not limited to, acrylamide, N-substituted acrylamide derivative, N,N-di-substituted acrylamide derivative, N-substituted methacrylamide derivative, and N,N-di-substituted methacrylamide derivative. These can be used alone or in combination.
  • water-soluble polymers having an amide group, an amino group, a hydroxyl group, a tetramethyl ammonium group, a silanol group, an epoxy group, etc. are obtained.
  • the water-soluble polymer having an amide group, an amino group, a hydroxyl group, a tetramethyl ammonium group, a silanol group, an epoxy group, etc. are advantageous to maintain the strength of an aqueous gel.
  • the proportion of the polymer there is no specific limitation to the proportion of the polymer and it can be suitably selected to suit to a particular application. It is preferably from 0.5 to 20 percent by mass to the total content of the hydrogel structure.
  • the mineral there is no specific limitation to the mineral and it can be suitably selected to suit to a particular application. Since the main component of the hydrogel is water, clay mineral is preferable and laminate clay minerals uniformly dispersible in water at the level of primary crystal are preferable and water swellable lamellar clay minerals are more preferable.
  • Such water swellable lamellar clay minerals have no particular limit and can be suitably selected to suit to a particular application. Examples include, but are not limited to, water swellable smectite and water swellable mica. These can be used alone or in combination. Of these, water swellable hectorite containing sodium as an interlayer ion, water swellable montmorillonite, water swellable saponite, and water swellable synthetic mica are preferable. Water swellable hectorite is more preferable because bolus having a high elasticity can be obtained. "Water swellable" means that water molecules are inserted between layers of lamellar clay mineral so that it can be dispersed in water.
  • the mineral can be appropriately synthesized or is commercially available.
  • the product commercially available are not particularly limited and can be suitably selected to suit to a particular application.
  • the proportion of the mineral is not particularly limited and can be suitably selected to suit to a particular application. For example, it is preferably from one percent by mass to 40 percent by mass and more preferably from 1 percent by mass to 25 percent by mass to the total content of a hydrogel structure in terms of modulus of elasticity and hardness of hydrogel structure.
  • water for example, deionized water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, and ultra pure water can be used.
  • an organic solvent can be added to enhance moisture retention of the hydrogel structure.
  • organic solvent is a water-soluble organic solvent.
  • the water-solubility of the water-soluble organic solvent means that the organic solvent is soluble in water in an amount of 30 percent by mass or more.
  • the water-soluble organic solvent is not particularly limited and can be suitably selected to suit to a particular application.
  • alkyl alcohols having one to four carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, amides such as dimethylformamide and dimethylacetoamide, ketones or ketone alcohols such as acetone, methylethylketone, and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, multi-valent polyols such as ethylene glycol, propylene glycol, 1,2-propane diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2,6-hexane triol, thioglycol, hexylene glycol, and glycerin, polyalkylene glycols such as polyethylene glycol, propylene glycol
  • the proportion of the organic solvent is preferably from 10 to 50 percent by mass to the total content of the hydrogel structure.
  • the proportion is not less than 10 percent by mass, the hydrogen is sufficiently prevented from being dried.
  • the proportion is not greater than 50 percent by mass, mineral is uniformly dispersed.
  • the other optional ingredients have no particular limit and can be suitably selected to suit to a particular application.
  • stabilizers surface treatment chemicals, polymerization initiators, colorants, viscosity modifiers, cohesion imparting agents, antioxidants, anti-aging agents, cross-linking promoters, ultraviolet absorbents, plasticizers, preservatives, dispersants, and surfactants.
  • the method of manufacturing a solid freeform fabrication product of the present disclosure is not particularly limited as long as a solid freeform fabrication product including the structure A and the structure B can be obtained.
  • One way of manufacturing the solid freeform fabrication product is molding a core imitating the hollow portion H, placing the core, infusing a precursor into the core, and taking out of the core after curing to obtain a structure like the shell mold molding.
  • such a structure can be directly fabricated using a 3D printer. Direct fabrication using a 3D printer is preferable to manufacture a structure having high quality with complicate and fine hollow portion H because this fabrication process obviates the need for removing the core.
  • the solid freeform fabrication product mentioned above is preferably manufactured by additive manufacturing (material jetting) in which a precursor (first liquid precursor) to obtain a soft material is discharged from an inkjet head followed by exposing the precursor to ultraviolet radiation.
  • a precursor first liquid precursor
  • the multi-material jetting method is preferable because it can change the material for a support from that for a model and remove the support in the post-processing.
  • One way of the post-processing is plasticization/liquefaction with heat or a solvent.
  • a preferable post-processing is to liquidize a support with heat. This processing optionally includes cleaning and other processes.
  • the solid freeform fabrication product is preferably manufactured by additive manufacturing in which a precursor (second liquid precursor) of a support forming material is discharged from an inkjet head followed by exposing the precursor to ultraviolet radiation. If the method of fabricating a model is different from the method of fabricating a support, the time for fabrication significantly increases. It is preferable to utilize ultraviolet radiation to cure a support forming material, which is the same manner as for the model material, to make the fabrication time per layer short.
  • the additive manufacturing process includes discharging a hydrogel forming material containing water and a polymerizable monomer and removing a support forming material to be removed later to form a layer formed of these materials.
  • the support forming material is applied to a site different from that of the hydrogel forming material and forms a support to support the hydrogel structure portion after it cures.
  • site different from that of the hydrogel liquid precursor means that the application position of the support forming material does not overlap the application position of the hydrogel forming material. Both materials may be adjacent to each other.
  • the method of applying the forming material as the additive manufacturing process has no particular limit as long as liquid droplets are applied to a target site with a suitable precision and it can be suitably selected to suit to a particular application.
  • a dispenser method, a spray method, and an inkjet printing method can be suitably selected to suit to a particular application.
  • Known devices are suitably used to execute these methods.
  • the dispenser method has an excellent quantitative property but difficulty in achieving a wide application area.
  • the spray method is capable of simply forming a fine discharging material, has a wide application area, and demonstrates excellent applicability but the quantitative property thereof is poor, which causes scattering due to the spray stream.
  • the inkjet printing method is particularly preferable.
  • the inkjet printing method has a good quantitative property in comparison with the spray method and a wider application area in comparison with the dispenser method. Accordingly, the inkjet printing method is preferable to accurately and efficiently form a complex solid shape.
  • nozzles capable of discharging the forming materials.
  • nozzles for use in a known inkjet printer can be suitably used.
  • Hydrogel Forming Material Hydrogel Forming Material
  • the hydrogel forming material contains water and a polymerizable monomer. It also preferably contains a mineral and an organic solvent and furthermore optionally includes a polymerizable monomer and other optional components.
  • the mineral As water, the mineral, the organic solvent, and the other optional components, the same as those for the hydrogel structure mentioned above can be used.
  • the polymerizable monomer includes a compound having at least one unsaturated carbon and carbon bond.
  • a polymerizable monomer polymerized upon application of active energy rays such as ultraviolet radiation and electron beams is preferable.
  • a mono-functional monomer and a polyfunctional monomer are suitable as the polymerizable monomer. These can be used alone or in combination.
  • the polyfunctional monomer includes, for example, a bi-functional monomer, a tri-functional monomer, and a tetra- or higher functional monomer.
  • the mono-functional monomer is a compound having a single unsaturated carbon-carbon bond.
  • Examples are acrylamides, N-substituted acrylamide derivatives, N,N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, N,N-disubstituted methacrylamide derivatives, and other mono-functional monomers. These can be used alone or in combination.
  • N-substituted acrylamide derivatives include, for example, N,N-dimethyl acryl amide (DMAA) and N-isopropyl acryl amide.
  • DMAA N,N-dimethyl acryl amide
  • N-isopropyl acryl amide N,N-dimethyl acryl amide
  • the mono-functional polymerizable monomer include, but are not limited to, 2-etylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, acryloylmorphorline (ACMO), caprolactone-modified tetrahydrofurfuryl(meta)acrylate, isobonyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, tetrahydro furfuryl(meth)acrylate, lauryl(meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl(meth)acrylate, isooctyl(meth)acrylate, tridecyl(meth)acrylate, caprolactone(meth)acrylate, ethoxyfied nonylphenol(meth)acrylate, and urethane(meth)acrylate. These can be used alone or in combination.
  • Water-soluble polymers having an amide group, an amino group, a hydroxyl group, a tetramethyl ammonium group, a silanol group, an epoxy group, etc. can be obtained by polymerizing the mono-functional monomers mentioned above.
  • Water-soluble polymers having an amide group, an amino group, a hydroxyl group, a tetramethyl ammonium group, a silanol group, an epoxy group, etc. are advantageous to maintain the strength of a blood vessel model.
  • bi-functional monomer examples include, but are not limited to, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxy pivalic acid ester di(meth)acrylate, hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonane diol(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, caprolactone-modified hydroxy pivalic acid neopent
  • tri-functional monomers include, but are not limited to, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tirallyl isocyanate, tris(2-hydroxyethyl)isocyanulate tri(meth)acrylate, ethoxyfied trimethylol propane tri(meth)acrylate, propoxyfied trimethylol propane tri(meth)acrylate, and propoxyfied glyceryl tri(meth)acrylate. These can be used alone or in combination.
  • tetra- or higher monomers include, but are not limited to, pentaerythritol tetra(meth)acrylate, ditrimethylol propanetetra(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, ethoxyfied pentaerythritol tetra (meth)acrylate, penta(meth)acrylate ester, and dipentaerythritol hexa(meth)acrylate. These can be used alone or in combination.
  • the proportion of the mono-functional monomer is not particularly limited and can be suitably selected to suit to a particular application. For example, it is preferably from 1 to 10 percent by mass and more preferably from 1 to 5 percent by mass to the total content of the hydrogel forming material. When the proportion is in the range of from 1 to 10 percent by mass, dispersion stability of the mineral in the hydrogel forming material is maintained and drawing property of a hydrogel structure is enhanced. The drawing property means that when a hydrogel structure is drawn, the hydrogel structure is not fractured (broken) but extended.
  • the proportion of the poly-functional monomer is preferably from 0.001 to 1 percent by mass and more preferably from 0.01 to 0.5 percent by mass to the total content of the hydrogel forming material.
  • the proportion is in the range of from 0.001 to 1 percent by mass, it is possible to control the modulus of elasticity and hardness of the obtained hydrogel structure in a suitable range.
  • the proportion of the polymerizable monomer is preferably from 0.5 to 20 percent by mass to the total content of the hydrogel forming material.
  • the proportion is from 0.5 to 20 percent by mass, the strength of the hydrogel structure can be closer to that of a human internal organ.
  • polymerization initiator There is no specific limitation to the polymerization initiator and it can be suitably selected to suit to a particular application.
  • Example are polymerization initiators and thermal polymerization initiators.
  • any material can be used which produces a radical upon irradiation of light (ultraviolet rays in a wavelength range of 220 to 400 nm).
  • the photopolymerization initiator has no particular limit and can be suitably selected to suit to a particular application.
  • acetophenone 2,2-diethoxyacetophenone, p-dimethylaminoacetone
  • benzophenone 2-chlorobenzophenone, p,p'-dichlorobenzophenone, p,p-bisdiethylamonobenzophenoen, Michler's Ketone
  • benzyl benzoin, benzoin methylether, benzoin ethylether, benzoin isopropylether, benzoin-n-propylether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, methylbenzoyl formate, 1-hydroxy cyclohexyl phenylketone,
  • the thermal polymerization initiator has no particular limitation and can be suitably selected to suit to a particular application.
  • examples thereof are azo-based initiators, peroxide initiators, persulfate initiators, and redox (oxidation-reduction) initiators. These can be used alone or in combination. Of these, peroxide initiators are preferable.
  • peroxide initiator there is no specific limitation to the peroxide initiator and it can be suitably selected to suit to a particular application.
  • potassium persulfate sodium persulfate, ammonium persulfate, peroxo sodium pyrosulfate, and peroxo potassium pyrosulfate. These can be used alone or in combination. Of these, potassium peroxo pyrosulfate is preferable.
  • the curing process includes exposing a predetermined region of the hydrogel forming material layer and the support forming material layer formed with the curing device to active energy rays to cure the region.
  • the curing device to cure the layers for example, an ultraviolet (UV) lamps, electron beams are used.
  • the curing device preferably includes a mechanism to remove ozone.
  • the UV lamp includes, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, and an ultraviolet light-emitting diode (UV-LED).
  • a high pressure mercury lamp for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, and an ultraviolet light-emitting diode (UV-LED).
  • UV-LED ultraviolet light-emitting diode
  • the ultra-high pressure mercury lamp is a point light source but if the DeepUV type combined with an optical system to have a high light use efficiency rate is used, the lamp is capable of emitting light in a short-wavelength range.
  • the metal halide lamp has a wide range of wavelength, it is suitable for colored materials.
  • Halogenated materials of metal such as Pb, Sn, and Fe are used therefor and can be selected to suit to absorption spectrum of a polymerization initiator.
  • the lamp for use in the curing has no particular limit and can be suitably selected to suit to a particular application. Lamps commercially available can be used. Examples are H lamp, D lamp, and V lamp (manufactured by Fusion System).
  • the emission wavelength of UV-LED is not particularly limited and can be suitably selected to suit to a particular application.
  • wavelengths of 365 nm, 375 nm, 385 nm, 395, nm and 405 nm are used.
  • short wavelength emission is advantageous to increase absorption of a polymerization initiator.
  • UV-LED is used as the UV lamp because it produces less heat.
  • the cured hydrogel material layer is preferably a hydrogel which contains water and ingredients soluble in the water in a three-dimensional network structure formed by complexing a polymer and a mineral.
  • the hydrogel has good expansibility and can be peeled off without breakage at once, so that the treatment after fabrication is significantly simplified.
  • the support is fabricated together with a solid freeform fabrication product to prevent degradation of fabrication property caused by dripping and flexure and removed in the end.
  • the support has no particular limit as long as it can support the hydrogel structure of the present disclosure. It is preferable to use a material having a solubility in a solvent or a material liquefied as a result of phase change by heating to remove the support present in the hollow portion after lamination. Since the hydrogel structure of the present disclosure is a hydrogel, it is preferable to avoid immersion in water to remove the support because the fabricated product may swell. For this reason, it is preferable to select a support forming material soluble in a solvent in which the hydrogel is not dissolved. In addition, the support forming material is preferably solid at 25 degrees C and is phase-changed into liquid at 50 degrees C. When the support forming material is a phase-changeable material, the support is readily removed after the hydrogel structure is formed.
  • the support forming material (core part forming material) used to support the inside of the hollow portion in the hydrogel structure of the present disclosure and the support forming material used to support the exterior of the structure can be the same or different from each other. Also, it is not necessary to fill the inside of the hollow portion with a support. Any minimal support is allowed which can support the hollow portion. Such a minimal support is efficient in comparison with a support which fills the entire of the inside of the hollow portion.
  • the support forming material contains a polymerizable monomer and other optional material such as a polymerization initiator and a colorant.
  • a polymerizable monomer such as polyethylene glycol dimethacrylate (PET), polyethylene glycol dimethacrylate (PET), polypropylene glycol dimethacrylate (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), sulfate, sulfate, sulfate, sulfate, styrene, acrylonitrile-sulfate, ethylene glycol dimethacrylate, poly(ethylene glycol dimethacrylate), poly(ethylene glycol dimethacrylate), polysulfate, polysulfate (PSS), polystyrenethacrylate (PSS-styrenethacrylate (PSS-styrenethacrylate (PSS-styrene (PSS-SSS-SSS-SS
  • the phase-changeable material includes, but is not limited to, liquid before it cures and solidified upon irradiation of active energy rays such as ultraviolet radiation like the case of the hydrogel.
  • the materials are suitable which are solid at room temperature (25 degrees C) and liquid at 60 degrees C.
  • a mono-functional ethylenic unsaturated monomer (A) (hereinafter referred to as monomer (A)) having a straight chain having 14 or more carbon atoms, a polymerization initiator (B), and a solvent (C) and more preferable to furthermore contain a solvent (D) in which the monomer (A) is poorly dissolved.
  • the mono-functional ethylenic unsaturated monomer (A) having a straight chain having 14 or more carbon atoms has no particular limit and can be suitably selected to suit to a particular application.
  • acrylate such as stearylacrylate and docosylacrylate
  • methacrylate such as stearylmethacrylate and docosylmethacrylate
  • acylamide such as palmityl acrylamide and starylacrylamide
  • vinyl such as vinylstearate and vinyl docosylate.
  • acrylates and acrylamide derivatives are preferable in terms of optical reactiveness and stearyl acrylates are more preferable to enhance solubility in a solvent.
  • Examples of the polymerization reaction of the monomer (A) are radical polymerization, ion polymerization, coordination polymerization, and ring-opening polymerization. Of these, in order to control polymerization reaction, radical polymerization is preferable. For this reason, the monomer (A) having a hydrogen bond power is preferably ethylenic unsaturated monomers. Of these, in terms of solubility, mono-functional ethylenic unsaturated monomers are preferable.
  • the polymerization initiator (B) has no specific limit and can be suitably selected to suit to a particular application. It includes thermal polymerization initiators and photopolymerization initiator. Of these, photopolymerization initiators are preferable to fabricate a solid freeform fabrication product.
  • the photopolymerization initiator it is possible to use any material which produces a radical at irradiation of light (in particular, ultraviolet radiation in a wavelength range of 220 to 400 nm).
  • the photopolymerization initiator include, but are not limited to, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p,p'-dichlorobenzophenone, p,p-bisdiethylamonobenzophenoen, Michler's Ketone, benzyl, benzoin, benzoin methylether, benzoin ethylether, benzoin isopropylether, benzoin-n-propylether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, methylbenzoyl formate, 1-hydroxy cyclo
  • the solvent (C) has no particular limit as long as the solvent (C) can dissolve the monomer (A) and can be suitably selected to suit to a particular application. In order to prevent a significant decrease of crystallinity of a polymer side chain, it is preferable to have a straight chain having six or more carbon atoms.
  • the solvent (C) having a straight chain having six or more carbon atoms include, but are not limited to, esters such as hexyl acetate and octyl acetate and alcohols such as hexanol, decanol, and dodecanol.
  • alcohol having a straight chain is preferable in order to enhance the support power to the modeling material of a cured object. It is possible to structure a hydrogen bond by a hydroxyl group while maintaining crystallinity of the polymer side chain.
  • alcohol having a straight chain having at least one hydroxyl group bonded to the primary carbon is preferable and 1-dodecanol is more preferable because it can prevent inhibition of crystallinity.
  • the solvent (D) is added in order to relieve the warpage of a support to be fabricated. If a solvent little or never soluble in a monomer is added, the internal stress occurring during curing is considered to be distributed.
  • the solvent (D) has no particular limit as long as it can little or never dissolve the monomer (A) and can be suitably selected to suit to a particular application.
  • the solvent (D) is preferably present as liquid compatible in a 60 degree C environment.
  • polyol that can remain in a cured object without inhibiting crystallinity of the polymer side chain and decrease viscosity as ink for supporting material is more preferable.
  • polystyrene resin examples include, but are not limited to, polyethers such as polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and butylene oxide, and polytetramethylene ether glycol (PTMEG), polyesters such as polycarprolactone diol (PCL), polycarbonate diol, and polyester polyol formed of polyol and polybasic acid, castor oil, and acrylic polyol. These can be used alone or in combination. Of these, polypropylene glycol is preferable.
  • polyethers such as polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and butylene oxide, and polytetramethylene ether glycol (PTMEG)
  • polyesters such as polycarpro
  • copolymer a block copolymer, a random copolymer, or a combination thereof can be used in combination.
  • the degree of polymerization of polyol has no particular limit and can be suitably selected to suit to a particular application.
  • the degree of polymerization is preferably from 10 to 10,000, more preferably from 100 to 5,000, and particularly preferably from 1,000 to 3,000.
  • the degree of polymerization is 10 or greater, the polyol is not vaporized at heating and can remain present in a cured object.
  • the degree of polymerization is 10,000 or less, the polyol can be present in liquid without excessively increasing viscosity at 60 degrees C.
  • the criteria of capability of dissolving the monomer (A) is determined based on whether the monomer (A) having a proportion of 1 percent by mass of the solvent can be dissolved therein. That is, the solvent (C) can dissolve the monomer (A) having 1 percent by mass or more of the dead weight of the solvent (C) while the solvent (D) cannot dissolve the monomer (A) having 1 percent by mass or more of the dead weight of the solvent (D).
  • the determination can be made whether or not non-dissolved monomer (A) remains after the monomer (A) at 1 percent by mass is loaded in the solvent (C) or the solvent (D) followed by stirring for 12 hours.
  • the support forming material preferably contains the mono-functional ethylenic unsaturated monomer (A) having a straight chain having 14 or more carbon atoms at a proportion of from 20 to 70 percent by mass and more preferably from 30 to 60 percent by mass.
  • the active energy ray curable liquid composition of the present disclosure preferably contains the polymerization initiator (B) in an amount of from 0.5 to 10 percent by mass and more preferably from 3 to 6 percent by mass.
  • the active energy ray curable liquid composition of the present disclosure preferably contains the solvent (C) that can dissolve the monomer (A) in an amount of from 20 to 70 percent by mass and more preferably from 30 to 60 percent by mass.
  • the active energy ray curable liquid composition of the present disclosure preferably contains the solvent (D) that can poorly dissolve the monomer (A) at a proportion of from 0 to 40 percent by mass and more preferably from 10 to 30 percent by mass.
  • the proportion is from 0 to 40 percent by mass, warpage of the support can be relieved while the support maintains its form. If the proportion is outside the range specified above, the support tends to be deformed due to the dead weight of the hydrogel structure and the external force applied during fabrication.
  • Wa represents the mass of the monomer (A)
  • Wc represents the mass of the solvent (C)
  • Wd represents the mass of the solvent (D).
  • the support forming liquid material For example, it is preferable to expose the support forming liquid material to ultraviolet radiation at an amount of 200 mJ/cm 2 or greater using an ultraviolet irradiator.
  • the same device as the device for use in curing the hydrogel structure can be used as the ultraviolet irradiator.
  • the temperature and humidity of a fabrication space be controlled from the beginning to the end of fabrication. This control is to prevent moisture absorption or drying of a fabricated object or solidification of a precursor.
  • the temperature is 25 degrees C or lower and the moisture is within -5 to +5 percent of a target RH value. It is more preferable when the target RH value is 95 percent.
  • the shielding structure may shield all the light or selectively shield ultraviolet radiation.
  • the monomer (A) When the monomer (A) is irradiated with ultraviolet radiation together with the polymerization initiator (B), the monomer (A) becomes a polymer and the solvent (C) is maintained in the polymer.
  • the polymer (A) is solidified when the carbon chain is arranged in a 25 degree C environment. If the solvent (C) is maintained in the polymer (A), contraction and warpage attributable to crystallization can be reduced.
  • the solvent (C) preferably has a straight chain having six or more carbon atoms in terms of curability.
  • the solvent (C) capable of dissolving the monomer (A) is preferably a non-reactive compound non-reactive to the polymerization initiator (B).
  • the solvent (C) capable of dissolving the monomer (A) means a solvent in which the monomer (A) is dissolved to form a uniform liquid.
  • the non-reactive compound is not chemically reactive even if it is exposed to ultraviolet radiation.
  • the solvent (C) is non-reactive, it does not react under the presence of a photopolymerization initiator so that polymerization reaction of monomers and crystallization of the polymer side chain are not inhibited. Therefore, the non-reactive solvent (C) is preferable.
  • the surface tension of the support forming material in the present disclosure has no particular limit and can be suitably selected to suit to a particular application.
  • the surface tension is preferably from 20 to 45 mN/m and more preferably from 25 to 34 mN/m at 25 degrees C.
  • the surface tension is 20 mN/m or greater, it is possible to prevent unstable jetting (such as deviation of jetting direction and no jetting) during fabrication.
  • the surface tension is 45 mN/m or less, a jetting nozzle for fabrication can be completely filled with liquid.
  • the surface tension can be measured by equipment such as a surface tensiometer (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., LTD.)
  • Viscosity at 25 degrees C of the support forming material in the present disclosure is preferably 1,000 mPa•s or less, more preferably 300 mPa•s or less, furthermore preferably 100 mPa•s or less, particularly preferably from 3 to 20 mPa•s, and most preferably from 6 to 12 mPa•s. With a viscosity surpassing 1,000 mPa•s, the support forming material may not be discharged even if a head is heated. Viscosity can be measured by, for example, a rotation viscometer (VISCOMATE VM-150 III, manufactured by TOKI SANGYO CO., LTD.) in a 25 degree C environment.
  • VISCOMATE VM-150 III manufactured by TOKI SANGYO CO., LTD.
  • the removing process is to remove a support including the pillar-like core part.
  • the pillar-like core part can be removed due to heating causing liquefaction and using a solvent in which the tubular portion is insoluble.
  • Being insoluble means that, for example, when 1 g of the tubular portion is mixed with 100 g of water at 30 degrees C and stirred, 90 percent by mass or more of the tubular portion is not dissolved in water.
  • Specific examples include, but are not limited to, a layer-smoothing process, a peeling-off process, discharging stabilizing process, a process of cleaning a fabricated object, and a process of polishing a fabricated object.
  • the method of manufacturing a solid freeform fabrication product of the present disclosure includes manufacturing a solid freeform fabrication product using the active energy ray curable liquid composition mentioned above and other optional processes.
  • the method of manufacturing a solid freeform fabrication product of the present disclosure includes laminating layers of the active energy ray curable liquid composition.
  • the active energy ray curable liquid composition is laminated to form a cured object forming a support portion and the support portion is removed by heating after the additive manufacturing.
  • the method may include furthermore optional process.
  • the device for manufacturing a solid freeform fabrication product in the present disclosure includes a container accommodating the active energy ray curable liquid composition, a discharging device to discharge the active energy ray curable liquid composition, a curing device to cure the active energy ray curable liquid composition discharged by the discharging device, and other optional devices.
  • the same active energy ray curable liquid composition (support forming material for use in the additive manufacturing process in the method of manufacturing the hydrogel structure) mentioned above can be used.
  • the cured object of the active energy ray curable liquid composition form a support portion and the hydrogel structure of the present disclosure form the model part in the additive manufacturing.
  • the container accommodating the active energy ray curable composition can be used as an ink cartridge and an ink bottle. This obviates the need for direct contact with ink in the operation of ink conveying, ink replacement, etc. so that contamination of fingers and clothes are prevented.
  • the container has no particular limit. Size, form, and material of the container can be suitably selected to suit to a particular application and usage. For example, it is preferable to use a light blocking material to block the light or cover the container with a light blocking sheet, etc.
  • FIG. 8 is a schematic diagram illustrating an example of the process of manufacturing a solid freeform fabrication product using a device for manufacturing a solid freeform fabrication product for use in the method of manufacturing the solid freeform fabrication product of the present disclosure.
  • a solid freeform fabrication device 10 includes head units 11 and 12 in which inkjet heads (forming material discharging device, discharging device) movable in both directions indicated by the arrows A and B and a fabricated object supporting substrate 14.
  • a hydrogel forming material is jetted from the head unit 12 and a support forming material is jetted from the head unit 11 on the fabricated object supporting substrate 14.
  • the hydrogel forming material is laminated while cured by a UV radiation irradiator (curing device) 13 disposed adjacent to the head unit.
  • the support forming material is jetted from the head unit 12 and solidified to form a first supporting layer having a pool part.
  • the hydrogel forming material is jetted from the head unit 11 to the pool part of the first supporting layer and irradiated with UV radiation to cure the hydrogel forming material.
  • the cured part is smoothed by a smoothing member 16 to form a first solid freeform fabrication product layer.
  • the support forming material is sprayed onto the first supporting layer and cured to stack a second supporting layer having a pool part.
  • the hydrogel forming material is sprayed onto the pool part of the second supporting layer followed by irradiation of UV radiation to stack a second solid freeform fabrication product layer on the first solid freeform fabrication product layer followed by smoothing to manufacture a solid freeform fabrication product 17.
  • the smoothing member having a roller form When the smoothing member having a roller form is used, it is preferable to reversely rotate the roller against the operation direction to ameliorate smoothing performance.
  • a stage 15 is lowered corresponding to the number of lamination to keep the gap constant between the head unit 11, the head unit 12, and the UV radiation irradiator 13 and the fabrication object 17 and a support 18.
  • the solid freeform fabrication device 10 may furthermore optionally include a mechanism for collecting and recycling the forming materials.
  • the solid freeform fabrication device 10 optionally includes a blade to remove the forming material attached to the nozzle surface and a detection mechanism to detect non-discharging nozzles. Moreover, it is preferable to control the environment temperature in the device during fabrication.
  • composition distribution and form control according to the state of a treatment site of a patient so that a blood vessel model or an internal organ model reflecting the form and property distribution peculiar to the patient.
  • the blood vessel forms of an affected part as a target of the catheter treatment and optionally a hardness distribution (composition distribution) of the blood vessels. Also in this case, the blood vessel is manufactured on the basis of the personal data of the patient.
  • One way of providing the composition distribution is to control the amount of the solvents contained in a hydrogel. This can be realized using a mechanism of discharging a plurality of compositions from respective inkjet heads utilizing the inkjet printing method described above.
  • a hydrogel forming material (hereinafter also referred to as liquid A) is discharged from a first head as a first liquid.
  • a solvent (hereinafter also referred to as liquid B) capable of diluting the hydrogel forming material and mainly composed of water and a solvent soluble in water, is discharged from a second head as a second liquid.
  • a support forming material used to form a hollow tube in a blood vessel model is discharged as a third liquid from a third head.
  • the liquid A and the liquid B are discharged from each inkjet head in a predetermined amount of printing and the ratio of the liquids jetted onto the same site can be precisely controlled.
  • surface data or solid data of a three-dimensional form designed by three dimensional computer-aided design (CAD) or taken in by a three-dimensional scanner or a digitizer are converted into Standard Template Library (STL) format, which is thereafter input into a additive manufacturing device.
  • CAD computer-aided design
  • STL Standard Template Library
  • compression stress distribution of the three dimensional form is measured.
  • compression stress distribution data of a three dimensional form is obtained by using MR Elastography (MRE) and thereafter input into the additive manufacturing device.
  • MRE MR Elastography
  • the mixing ratio of the liquid A and the liquid B to be discharged to sites corresponding to the data of a three-dimensional form is determined.
  • the direction of the fabrication of a three-dimensional form to be fabricated is determined.
  • the fabrication direction is not particularly limited. Normally, the direction is chosen such that the Z direction (height direction) is the lowest.
  • the projected areas on X-Y plane, X-Z plane, and Y-Z plane of the three-dimensional form are obtained.
  • the thus-obtained block form is sliced in the Z direction with a thickness of a single layer.
  • the thickness of a layer changes depending on the material and is normally from 20 to 60 ⁇ m.
  • this block form is disposed in the center of the Z stage (i.e., table on which the product lifted down layer by layer for each layer forming is placed).
  • the block forms are arranged on the Z stage.
  • the block forms can be piled up. It is possible to automatically create these block forms, the slice data (contour line data), and the placement on the Z stage if materials to be used are determined.
  • FIG. 9 is a schematic diagram illustrating an example in which the first liquid and the second liquid are mixed according to a liquid discharging method.
  • Individual heads ⁇ and ⁇ (illustrated in FIG. 8 ) are moved bi-directionally and discharge the liquid A and the liquid B to determined regions in a determined amount ratio to form a dot.
  • the liquid A and the liquid B can be mixed in the dot as illustrated in FIG. 10 to obtain the pre-determined mixing ratio (liquid “A”: liquid “B”).
  • such dots are continuously formed to form a liquid mixture film of the liquid A and the liquid B having the pre-determined mass ratio in the pre-determined area.
  • the liquid mixture film is irradiated with ultraviolet (UV) radiation and cured to form a hydrogel film (layer) having the pre-determined ratio in the pre-determined region as illustrated in FIG. 9 .
  • UV ultraviolet
  • the stage ( FIG. 9 ) is lowered in an amount corresponding to the thickness of the single layer.
  • the dots are continuously formed on the hydrogel film to form a liquid mixture film of the liquid A and the liquid B having a pre-determined mass ratio in pre-determined regions.
  • the liquid film of the liquid A and the liquid B is exposed to UV radiation and cured to form a hydrogel film. This lamination is repeated to form a three-dimensional object.
  • the thus-fabricated three-dimensional object has different mass ratios of liquid A and liquid B in the solid hydrogel of the liquid film illustrated in FIG. 8 so that modulus of elasticity therein can be continuously changed. If the mixing ratio pattern is adjusted for each cross section layer, a hydrogel structure partially having an arbitrary physical property can be obtained.
  • the UV radiation irradiator is disposed next to an inkjet head to jet a hydrogel forming material to save time to be taken for smoothing treatment, thereby speeding up the fabrication.
  • the hydrogel structure for use in the present disclosure can be arbitrarily changed in hardness using the same material if the composition ratio thereof is changed by the combination of the hydrogel forming material and diluting fluid. For this reason, in the case of fabrication according to an inkjet printing method, it is easy to provide the hardness distribution of a blood vessel based on personal data if the ratio of both is changed using a plurality of inkjet heads.
  • the hydrogel includes a massive amount of water and has a composition extremely close to a human body. Also, the texture thereof is very close as well. If this is used in combination with 3D printing, it is very useful to form a blood vessel model.
  • hydrogel structure, the blood vessel model, and the internal organ model of the present disclosure can be manufactured by utilizing 3D printing technologies, a model reproducing the form and the property can be manufactured on the basis of the data of the diseased part of a patient. For this reason, it is suitable to use it for a simulation for delicate surgery.
  • the solid freeform fabrication product of the present disclosure has a feature of having a hollow part.
  • the hollow tubular structure is formed using the support forming material as described above. It is preferable to use a solid material that is phase-changed into liquid by heat as the support forming material.
  • the support forming material used is preferably colored in red like blood by a colorant.
  • the blood vessel model and the internal organ model can be used in the training for surgical procedures with surgical tools such as ultrasonic wave knife and electrosurgical knife. More specifically, in the training of dissecting the site near the blood vessel disposed in an internal organ model, it can be used as an internal organ model from which blood bleeds if the blood vessel is mistakenly damaged.
  • Data for the hollow portion H is created on the basis of data of aortic valve and coronary artery.
  • Aortic valve with coronary arteries 3D model created by Surgen Pro and available from Turbosquad was used as the data and selected in any range.
  • the selected data is resized into 108 ⁇ 85 ⁇ 45 mm.
  • the obtained data was divided into that for aortic valve portion V and coronary artery portion C1 with the hollow portion of the coronary artery portion C1 filled. This data was defined as the data of a coronary artery portion C2 (hollow portion H).
  • Data was created to add a thickness of 2 mm to the coronary artery portion C2.
  • the created data was defined as the data for a coronary artery portion C3.
  • the data of the coronary artery portion C2 was booleaned from the data of the coronary artery portion C3 to create data for the tubular portion. This created data was defined as the data for a coronary artery portion C4.
  • the structure A and the aortic valve portion V were smoothly connected (merged) while piercing the entrance of the hollow portion of the coronary artery portion C4 and the coronary artery of the aortic valve portion V.
  • From top of the structure A was determined. "From top” was the direction in which the aortic valve on the side of the heart was exposed. A pedestal was structured on the basis of this direction to obtain the data of the structure A and the data of the structure B. Refer to "Form of Structure B That Holds Structure A" described above for creation of the data of the Structure B.
  • the form of the coronary artery portion C2 (hollow portion H) was output using a procured 3D printer (POLYGET, manufactured by Stratasys Ltd.) and molded using a silicone resin (KE-12, manufactured by Shin-Etsu Chemical Co., Ltd.). After the resin was completely cured, a sprue was provided to this mold. The mold was warmed in a hot bath at 80 degrees C for one hour. Molten wax (TOYO TECHNICAL WAX, HARD RED, manufactured by TOYO CHEMICAL LABORATORIES, INC.) was charged int the mold. The mold was placed in a thermostatic chamber at 120 degrees C and allowed to rest for eight hours followed by cooling down to cure the wax. The cured wax was taken out of the mold and the unwanted part such as burr of the wax was removed to obtain a core I made of wax with a form following the coronary artery portion C2.
  • a procured 3D printer POLYGET, manufactured by Stratasys Ltd.
  • Molds of the structure A and the Structure were manufactured.
  • the data of the structure A and the structure B were output by a 3D printer and the molds thereof were obtained using a silicone resin to obtain silicone resin molds.
  • the obtained mold of the structure A and the obtained mold of the structure B were defined as mold Ma and Mold Mb, respectively.
  • a releasing agent ("BARRIER COAT No. 7", manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the inside of the mold Ma and the core I made of wax was fixed onto a appropriate site of the mold Ma.
  • a polyurethane precursor (HITOHADA® gel (transparent) hardness C7, manufactured by EXSEAL Co., Ltd.) was poured into the mold Ma from the sprue. The polyurethane precursor was sufficiently defoamed by stirring the main agent and a curing agent. After the precursor was sufficiently cured, the precursor was taken out of the mold Ma and placed in hot water at 65 degrees C to melt the core I made of wax.
  • a liquid mixture of a coating agent (surface coating agent, manufactured by EXSEAL Co., Ltd.) and butyl acetate at a ratio of 1:1) was applied to the surface to obtain a structure A1 (moisture content: 0 percent, shore A hardness of 3).
  • a releasing agent (“BARRIER COAT No. 7", manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the inside of the mold Mb.
  • a polyurethane precursor (HITOHADA® gel (transparent) hardness C7) was poured into the mold Mb from the sprue. The polyurethane precursor was sufficiently defoamed by stirring the main agent and a curing agent. The polyurethane precursor was sufficiently cured at room temperature and taken out of the mold Mb.
  • a liquid mixture of a coating agent surface coating agent, manufactured by EXSEAL Co., Ltd.
  • the structure A1 was inserted into and integrated with the structure B1 to obtain a set of the structure A1 and the structure B1.
  • the structure A1 or the set of the structure A1 and the structure B1 was placed on a glass plate (Blue (soda) glass, manufactured by AS ONE Corporation) and compared with the form on the data and evaluated the difference regarding the deformation by dead weight.
  • the site where the difference was visible was measured with a ruler or caliper to analyze the degree of the error.
  • a catheter was inserted into the coronary artery of the structure A1.
  • the hollow portion H was viewed from top through the structure A1, how the gold marker attached to the catheter looked was checked.
  • a catheter was inserted into the coronary artery of the structure A1.
  • the hollow portion H was viewed at 60 degrees shifted from top through the structure A1, how the gold marker attached to the catheter looked was checked.
  • At least 10 portions were selected from the tubular portions of the fabrication product A and the film thickness at three points of each portion of from top and 60 degrees from top was measured. The average, the maximum, and the minimum of the measurements are shown in Table 1.
  • the core I and the mold Mb were fixed with a cyanoacrylate-based glue (ARON ALPHA, manufactured by TOAGOSEI CO., LTD.) and a releasing agent was applied to the entire of both.
  • the structure was placed in the polypropylene container (ZIPLOC, 480 ml, manufactured by Asahi Kasei Home Products Corporation) and 500 g of polyurethane precursor (HITOHADA® gel (transparent) hardness C7, manufactured by EXSEAL Co., Ltd.) in which the main agent and a curing agent were mixed was poured into the container to adjust the position of the core I.
  • the core I and the mold Mb were not in contact with the container. Also, the core I was not exposed to the liquid surface and part of the mold Mb was exposed to the liquid surface at this point.
  • Hard material (VERO CLEAR, manufactured by Stratasys Ltd.) was output on the basis of the structure data A with a 3D printer available on the market to obtain a structure A102 (moisture content: 0 percent, shore hardness A of 100 of cured product).
  • the structure A102 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Comparative Example 1 readily deformed on its own because it did not have a structure B1.
  • the front of the blood vessel deformed by dead weight so that the branch angle significantly changed.
  • the thickness to the hollow portion from top increased so that visibility deteriorated when the catheter was inserted into the hollow portion. This deterioration was significant when the structure A was viewed from the oblique direction.
  • Comparative Example 3 did not deform on its own unlike comparative Example 1. However, it does not deform by an external force, so that the texture was significantly different from that of a live body when a catheter was inserted.
  • the coronary artery portion C2, coronary artery portion C3, aortic valve portion V, and the pedestal P1 and the cuboid R2 based on the structure A data were created in the same manner as in Example 1. Refer to "Form of Structure B That Holds Structure A" described above for creation of the pedestal P1 and the cuboid R2.
  • Soft material (AGILUS 30, manufactured by Stratasys Ltd.) was output on the basis of the structure data AB with a 3D printer available on the market to obtain a structure AB1 (moisture content: 0 percent, shore hardness A of 32 of cured product).
  • the structure AB1 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • the structure AB1 shows good results about deformation by dead weight, deformation by external force, visibility from top, and visibility from oblique direction like Example 1. Moreover, there is no need for integrating the structure A and the structure B because the structure A and the structure B were integrally fabricated by material jetting. It is possible to readily obtain fabrication objects with a good accuracy because the structure AB1 was output with a 3D printer.
  • the core I made of wax with a form of the coronary artery portion C2, the mold Ma as a set of the structure A mold, and the mold Mb as a set of the obtained structure B were manufactured in the same manner as in Example 1.
  • a total of 15 g of agar powder (cool agar, produced by Nitta Gelatin Inc.) was slowly added dropwise at room temperature to 465 g of deionized water (also referred to as pure water) during stirring the deionized water.
  • the core I made of wax was fixed onto an appropriate site in the mold Ma and the hydrogel precursor 1 was poured from the sprue and allowed to rest at 4 degrees C for 24 hours. After the hydrogel precursor 1 was completely cured, it was taken out from the mold. The core I was extruded and removed to obtain a structure A2 (moisture content: 96.9 percent, shore A hardness of 0 of cured product).
  • the hydrogel precursor 1 was poured from the sprue of the mold Mb and allowed to rest at 4 degrees C for 24 hours.
  • hydrogel precursor 1 After the hydrogel precursor 1 was sufficiently cured, it was taken out from the mold to obtain a structure B2 (moisture content: 96.9 percent, shore A hardness of 0 of cured product).
  • the structure A2 was inserted into and integrated with the structure B2 to obtain a set of the structure A2 and the structure B2.
  • the set of the structure A2 and the structure B2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • the set of the structure A2 and the structure B2 shows good results about deformation by dead weight, deformation by external force, visibility from top, and visibility from oblique direction like Example 1.
  • the texture of the structure A was close to that of a live body when a catheter was inserted because the structure A was made of hydrogel.
  • hydrogel precursor 2 20.0 parts of glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and 0.8 parts of N,N,N',N'-tetramethylethylene diamine (manufactured by Tokyo Chemical Industry Co. Ltd.) were admixed to obtain a hydrogel precursor 2.
  • a mold of the structure AB was manufactured.
  • the form of the structure data AB was output by a 3D printer and the mold thereof was obtained using a silicone resin to obtain silicone resin mold Mab.
  • the core I made of wax was fixed onto an appropriate site in the mold Mab.
  • a total of 197.8 parts of the hydrogel precursor 2 was prepared and 1.2 parts of peroxo potassium pyrosulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was poured thereto to melt the hydrogel precursor 2.
  • the obtained liquid was poured into the sprue of the mold Mab and allowed to rest at room temperature for 24 hours under a sealed condition. After the liquid was completely cured, it was taken out from the mold.
  • the core I was rinsed away with hexane heated to 60 degrees C to obtain a structure AB2 (moisture content: 60.6 percent, shore A hardness of 0 of cured product).
  • the obtained structure AB2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • the structure AB2 shows good results about deformation by dead weight, deformation by external force, visibility from top, and visibility from oblique direction like Example 1. It is not necessary to combine the structure A and the structure B because both are integrated. The structure is not affected by melting the core with heat because the hydrogel constituting the structure A and the structure B does not change the phase by heat.
  • Solvent (C) manufactured by Tokyo Chemical Industry Co. Ltd.
  • Solvent (D) polypropylene glycol 2000
  • Solvent (A) manufactured by Tokyo Chemical Industry Co. Ltd.
  • IRGACURE 819 Polymerization initiator (B), manufactured by BASF)
  • the hydrogel precursor 3 and the precursor of support forming material were discharged using the fabrication device illustrated in FIG. 8 on the basis of the structure data AB and exposed to UV radiation to cure the materials. This process was repeated to obtain a laminated fabrication product.
  • the laminated fabrication product was allowed to rest in a thermostatic chamber at 50 degrees C for 30 minutes to liquidize and remove the support.
  • the pillar-like core part remaining was rinsed away with lukewarm water at 50 degrees C to obtain a structure AB3 (moisture content: 60.6 percent, shore A hardness of 0 of cured product).
  • the obtained structure AB3 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • the structure AB3 shows good results about deformation by dead weight, deformation by external force, visibility from top, and visibility from oblique direction like Example 1. Moreover, there is no need for integrating the structure A and the structure B because the structure A and the structure B are integrally fabricated by material jetting. It is possible to readily obtain fabrication objects with a good accuracy because the structure AB3 was output with a 3D printer. The structure is not affected by melting the support with heat because the hydrogel constituting the structure A and the structure B does not change the phase by heat.
  • the present disclosure relates to the solid freeform fabrication product of the following 1 and also includes the following 2 to 7 as embodiments.

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JP2018178069A (ja) 2016-08-31 2018-11-15 株式会社リコー ハイドロゲル構造体、その製造方法、活性エネルギー線硬化型液体組成物、及び用途
CN110302428A (zh) * 2019-07-30 2019-10-08 中国人民解放军陆军军医大学第一附属医院 基于活细胞3d打印的软骨-骨-骨髓复合组织结构及方法

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JPS5140857B2 (fr) 1971-12-29 1976-11-06
WO2006083963A2 (fr) * 2005-02-03 2006-08-10 Christopher Sakezles Modeles et procedes mettant en oeuvre ces modeles pour l'essai de dispositifs medicaux
JP2009273508A (ja) 2008-05-12 2009-11-26 Ono Kogyo:Kk 手術シミュレーション用軟質血管モデルの製造方法
US20130102690A1 (en) * 2011-10-21 2013-04-25 Nitta Casings Inc. Collagen-polysaccharide materials mimicking blood vessels, tissues and bones for medical, pharmaceutical and orthopedic applications, and processes for producing the same
JP2015069054A (ja) 2013-09-30 2015-04-13 ファインバイオメディカル有限会社 カテーテル治療シミュレータ
JP6385664B2 (ja) 2013-09-30 2018-09-05 ファインバイオメディカル有限会社 カテーテル治療シミュレータ
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